Platinum group alloys have an excellent electronic structure for oxidation of alcohols,but the active sites are more susceptible to deactivation by CO adsorbates(CO_(ads)).The precise integration of single-atom and al...Platinum group alloys have an excellent electronic structure for oxidation of alcohols,but the active sites are more susceptible to deactivation by CO adsorbates(CO_(ads)).The precise integration of single-atom and alloy structures is highly attractive for energy conversion but still a challenge.Here,we report an ionexchange coupled in situ reduction strategy to fabricate hollow PtPdTe alloy nanoreactors loaded with atomically dispersed Cu sites(Cu_(SA)/h-PtPdTe NRs).The planted oxyphilic Cu single sites and resulted compressive strains are conductive to modulating the electronic structure of the active sites,which changes the rate-determining step of the reaction while inhibiting the formation of CO_(ads)and modulating the adsorption of intermediates,resulting in the improved activity and stability.Specifically,the obtained Cu_(SA)/h-PtPdTe NRs exhibit an excellent oxidation performance of multiple alcohols,especially for methanol and ethanol,with 8.0 and 10.3 times of the mass activity higher than Pt/C,and the activity could be recovered by refreshing the electrolyte and could be sustained for 72,000 and 36,000 s,respectively.Meanwhile,Cu_(SA)/h-PtPdTe NRs show superior oxidation performance and durability to ethylene glycol and glycerol.This work pioneers the realization of precise modulation of catalytic sites using single atoms and provides an encouraging pathway for the design of efficient and stable electrocatalysts for the oxidation of multiple alcohols,which could broaden the range of options and sources of fuel cells.展开更多
Nitrous oxide（N_2O） is a potent greenhouse gas that can be emitted during biological nitrogen removal. N_2O emission was examined in a multiple anoxic and aerobic process at the aeration rates of 600 m L/min sequenc...Nitrous oxide（N_2O） is a potent greenhouse gas that can be emitted during biological nitrogen removal. N_2O emission was examined in a multiple anoxic and aerobic process at the aeration rates of 600 m L/min sequencing batch reactor（SBRL） and 1200 m L/min（SBRH）.The nitrogen removal percentage was 89% in SBRLand 71% in SBRH, respectively. N_2O emission mainly occurred during the aerobic phase, and the N_2O emission factor was 10.1%in SBRLand 2.3% in SBRH, respectively. In all batch experiments, the N_2O emission potential was high in SBRLcompared with SBRH. In SBRL, with increasing aeration rates, the N_2O emission factor decreased during nitrification, while it increased during denitrification and simultaneous nitrification and denitrification（SND）. By contrast, in SBRHthe N_2O emission factor during nitrification, denitrification and SND was relatively low and changed little with increasing aeration rates. The microbial competition affected the N_2O emission during biological nitrogen removal.展开更多
Dense monolithic(Ti,Zr,Hf)C/SiC ceramic nanocomposites with four different molar ratios of metallic elements in the(Ti,Zr,Hf)C phase(i.e.,Ti:Zr:Hf=1:1:1,2:3:5,2:3:3,and 1:2:1)were prepared upon pyrolysis of novel(Ti,Z...Dense monolithic(Ti,Zr,Hf)C/SiC ceramic nanocomposites with four different molar ratios of metallic elements in the(Ti,Zr,Hf)C phase(i.e.,Ti:Zr:Hf=1:1:1,2:3:5,2:3:3,and 1:2:1)were prepared upon pyrolysis of novel(Ti,Zr,Hf)-containing single-source precursors(SSPs),followed by spark plasma sintering(SPS).A thorough characterization was conducted to elucidate the synthesis of the SSPs,polymer-to-ceramic transformation,chemical/phase compositions,and microstructure of the SiTiZrHfC-based ceramics.The results revealed the feasibility of synthesizing nanocomposites with high(Ti,Zr,Hf)C contents using the SSP method.These nanocomposites were characterized by a unique microstructure with in situ generated(Ti,Zr,Hf)C@C core-shell nanoparticles homogeneously mixed withβ-SiC.The ablation behavior of the nanocomposites was evaluated on an air-plasma device for 60 s.Impressively,the nanocomposites exhibited excellent ablation resistance,and the lowest linear ablation rate reached−0.58μm/s at 2200°C.Notably,the ablation resistance can be dramatically improved by precisely tailoring the atomic ratios of metal elements within the(Ti,Zr,Hf)C phase via the molecular design of the SSPs.The formation of a multiple-oxide layer with both a high-meltingpoint phase((Ti,Zr,Hf)O_(2))and low-melting-point phases((Zr,Hf)TiO_(4))and glassy SiO_(2),as well as their structure,played a critical role in the enhanced ablation resistance.The uniform distribution of the high-melting-point(Ti,Zr,Hf)O_(2)nano/microparticles throughout the glassy SiO_(2)matrix significantly enhanced the viscosity and stability of the oxide layer by the pinning effect,offering superior protection against the ingress of oxygen atoms and excellent resistance to mechanical erosion.展开更多
基金supported by the National Natural Science Foundation of China(22102132)the Funds for Basic Scientific Research in Central Universities+2 种基金the Scientific Research Foundation of Qingdao UniversityTaishan Scholar Program(NO.tsqnz20231213)sponsored by the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University(CX2024101)。
文摘Platinum group alloys have an excellent electronic structure for oxidation of alcohols,but the active sites are more susceptible to deactivation by CO adsorbates(CO_(ads)).The precise integration of single-atom and alloy structures is highly attractive for energy conversion but still a challenge.Here,we report an ionexchange coupled in situ reduction strategy to fabricate hollow PtPdTe alloy nanoreactors loaded with atomically dispersed Cu sites(Cu_(SA)/h-PtPdTe NRs).The planted oxyphilic Cu single sites and resulted compressive strains are conductive to modulating the electronic structure of the active sites,which changes the rate-determining step of the reaction while inhibiting the formation of CO_(ads)and modulating the adsorption of intermediates,resulting in the improved activity and stability.Specifically,the obtained Cu_(SA)/h-PtPdTe NRs exhibit an excellent oxidation performance of multiple alcohols,especially for methanol and ethanol,with 8.0 and 10.3 times of the mass activity higher than Pt/C,and the activity could be recovered by refreshing the electrolyte and could be sustained for 72,000 and 36,000 s,respectively.Meanwhile,Cu_(SA)/h-PtPdTe NRs show superior oxidation performance and durability to ethylene glycol and glycerol.This work pioneers the realization of precise modulation of catalytic sites using single atoms and provides an encouraging pathway for the design of efficient and stable electrocatalysts for the oxidation of multiple alcohols,which could broaden the range of options and sources of fuel cells.
基金supported by the Shenzhen Overseas High-Level Talents Innovation Funds Peacock Plan Project (No. KQCX20120814155347053)the National Natural Science Foundation of China (No. 51108242)
文摘Nitrous oxide（N_2O） is a potent greenhouse gas that can be emitted during biological nitrogen removal. N_2O emission was examined in a multiple anoxic and aerobic process at the aeration rates of 600 m L/min sequencing batch reactor（SBRL） and 1200 m L/min（SBRH）.The nitrogen removal percentage was 89% in SBRLand 71% in SBRH, respectively. N_2O emission mainly occurred during the aerobic phase, and the N_2O emission factor was 10.1%in SBRLand 2.3% in SBRH, respectively. In all batch experiments, the N_2O emission potential was high in SBRLcompared with SBRH. In SBRL, with increasing aeration rates, the N_2O emission factor decreased during nitrification, while it increased during denitrification and simultaneous nitrification and denitrification（SND）. By contrast, in SBRHthe N_2O emission factor during nitrification, denitrification and SND was relatively low and changed little with increasing aeration rates. The microbial competition affected the N_2O emission during biological nitrogen removal.
基金the National Natural Science Foundation of China(Nos.52102085 and 52072410)the National Natural Science Fund for Excellent Young Scholars(Overseas)the State Key Laboratory of Powder Metallurgy,Central South University,China(No.621022335)for financial support.
文摘Dense monolithic(Ti,Zr,Hf)C/SiC ceramic nanocomposites with four different molar ratios of metallic elements in the(Ti,Zr,Hf)C phase(i.e.,Ti:Zr:Hf=1:1:1,2:3:5,2:3:3,and 1:2:1)were prepared upon pyrolysis of novel(Ti,Zr,Hf)-containing single-source precursors(SSPs),followed by spark plasma sintering(SPS).A thorough characterization was conducted to elucidate the synthesis of the SSPs,polymer-to-ceramic transformation,chemical/phase compositions,and microstructure of the SiTiZrHfC-based ceramics.The results revealed the feasibility of synthesizing nanocomposites with high(Ti,Zr,Hf)C contents using the SSP method.These nanocomposites were characterized by a unique microstructure with in situ generated(Ti,Zr,Hf)C@C core-shell nanoparticles homogeneously mixed withβ-SiC.The ablation behavior of the nanocomposites was evaluated on an air-plasma device for 60 s.Impressively,the nanocomposites exhibited excellent ablation resistance,and the lowest linear ablation rate reached−0.58μm/s at 2200°C.Notably,the ablation resistance can be dramatically improved by precisely tailoring the atomic ratios of metal elements within the(Ti,Zr,Hf)C phase via the molecular design of the SSPs.The formation of a multiple-oxide layer with both a high-meltingpoint phase((Ti,Zr,Hf)O_(2))and low-melting-point phases((Zr,Hf)TiO_(4))and glassy SiO_(2),as well as their structure,played a critical role in the enhanced ablation resistance.The uniform distribution of the high-melting-point(Ti,Zr,Hf)O_(2)nano/microparticles throughout the glassy SiO_(2)matrix significantly enhanced the viscosity and stability of the oxide layer by the pinning effect,offering superior protection against the ingress of oxygen atoms and excellent resistance to mechanical erosion.
